Connecting defects and amorphization in UiO-66 and MIL-140 metal-organic frameworks: a combined experimental and computational study

The mechanism and products of the structural collapse of the metal-organic frameworks (MOFs) UiO-66 , MIL-140B and MIL-140C upon ball-milling are investigated through solid state 13 C NMR and pair distribution function (PDF) studies, finding amorphization to proceed by the breaking of a fraction of...

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Published in:Physical chemistry chemical physics : PCCP 2016-01, Vol.18 (3), p.2192-221
Main Authors: Bennett, Thomas D, Todorova, Tanya K, Baxter, Emma F, Reid, David G, Gervais, Christel, Bueken, Bart, Van de Voorde, B, De Vos, Dirk, Keen, David A, Mellot-Draznieks, Caroline
Format: Article
Language:English
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Summary:The mechanism and products of the structural collapse of the metal-organic frameworks (MOFs) UiO-66 , MIL-140B and MIL-140C upon ball-milling are investigated through solid state 13 C NMR and pair distribution function (PDF) studies, finding amorphization to proceed by the breaking of a fraction of metal-ligand bonding in each case. The amorphous products contain inorganic-organic bonding motifs reminiscent of the crystalline phases. Whilst the inorganic Zr 6 O 4 (OH) 4 clusters of UiO-66 remain intact upon structural collapse, the ZrO backbone of the MIL-140 frameworks undergoes substantial distortion. Density functional theory calculations have been performed to investigate defective models of MIL-140B and show, through comparison of calculated and experimental 13 C NMR spectra, that amorphization and defects in the materials are linked. Ball-milling amorphization of UiO-66, MIL-140B and MIL-140C was observed to proceed by metal-ligand bond breaking, and linked to the generation of successive defects.
ISSN:1463-9076
1463-9084
DOI:10.1039/c5cp06798g